Liquid crystal compounds having a terminal 1-alkynyl residue

ABSTRACT

Compounds of the formula ##STR1## wherein n stands for the number 0 or 1; rings A, B and C each independently represent trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl or unsubstituted or fluoro-substituted 1,4-phenylene; R 1  denotes 3E-alkenyl with 4 to 12 carbon atoms, 4-alkenyl with 5 to 12 carbon atoms or, when ring A represents trans-1,4-cyclohexylene or trans-1,3-dioxane-2,5-diyl, also 1E-alkenyl with 2 to 12 carbon atoms; and R 2  is hydrogen or C 1  -C 10  -alkyl, their manufacture as well as liquid crystalline mixtures which contain such compounds and their use for electro-optical purposes.

This is a division of application Ser. No. 07/579,905 filed Sep. 10,1990, now U.S. Pat. No. 5,171,473.

FIELD OF THE INVENTION

The present invention is concerned with novel compounds having aterminal 1-alkynyl residue, their manufacture, liquid crystallinemixtures which contain such compounds and their use for electro-opticalpurposes.

BACKGROUND OF THE INVENTION

Liquid crystals are used primarily as dielectrics in indicating devices,since the optical properties of such substances can be influenced by anapplied voltage. Electro-optical devices based on liquid crystals arewell-known to the person skilled in the art and can be based on variouseffects. Such devices are, for example, cells having dynamic scattering,DAP cells (deformation of aligned phases), guest/host cells, TN Cellshaving a twisted nematic structure, STN cells ("super-twisted nematic"),SBE cells ("super-birefringence effect") and OMI cells ("optical modeinterference"). The most common indicating devices are based on theSchadt-Helfrich effect and have a twisted nematic structure.

The liquid crystal materials must have a good chemical and thermalstability and a good stability towards electric fields andelectromagnetic radiation. Further, at the usual operating temperaturesthey should have a suitable mesophase in as broad a range as possible(for example a nematic or a cholesteric phase for the cells referred toabove), but nevertheless should have a sufficiently low viscosity and inthe cells should give rise to short response times, low thresholdpotentials and a high contrast. Further properties such as theelectrical conductivity, the dielectric anisotropy and the opticalanisotropy must fulfil different requirements depending on the field ofapplication and type of cell. For example, materials for cells having atwisted nematic structure should have a positive dielectric anisotropyand an electrical conductivity which is as low as possible.

In order to fulfil these to some extent contradictory requirements, itis generally necessary to produce mixtures having up to about 15components. It is therefore important that the components have a goodmiscibility with one another and a sufficient solubility.

In order to achieve sufficiently broad mesophase ranges, it is usuallynecessary to add clearing point-increasing components to the mixtures,but in this case the viscosity and the electro-optical properties can beinfluenced disadvantageously. Further, materials having a low opticalanisotropy, which are of interest e.g. for actively-addressed liquidcrystal indicators, frequently produce smectic tendencies and usuallyalso lead to an increase in the threshold potential, in the viscosityand/or in the response times. Furthermore, non-polar materials having ahigh optical anisotropy often have only smectic mesophases or even noliquid crystalline properties.

SUMMARY OF THE INVENTION

The invention is concerned with compounds of formula ##STR2## wherein nstands for the number 0 or 1; rings A, B and C each independentlyrepresent trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl orunsubstituted or fluoro-substituted 1,4-phenylene; R¹ is a 3E-alkenylwith 4 to 12 carbon atoms, a 4-alkenyl with 5 to 12 carbon atoms or whenring A represents trans-1,4-cyclohexylene or trans-1,3-dioxane-2,5-diyl, also a 1E-alkenyl with 2 to 12 carbon atoms; and R² is hydrogenor C₁ -C₁₀ -alkyl.

DETAILED DESCRIPTION OF THE INVENTION

The invention is concerned with compounds of formula ##STR3## wherein nstands for the number 0 or 1; rings A, B and C each independentlyrepresent trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl orunsubstituted or fluoro-substituted 1,4-phenylene; R¹ is a 3E-alkenylwith 4 to 12 carbon atoms, a 4-alkenyl with 5 to 12 carbon atoms or whenring A represents trans-1,4-cyclohexylene or trans-1,3-dioxane-2,5-diyl, also a 1E-alkenyl with 2 to 12 carbon atoms; and R² is hydrogenor C₁ -C₁₀ -alkyl.

The compounds in accordance with the invention are non-polar compoundswith comparatively very broad mesophase ranges, high clearing points anda pronounced nematic tendency. In spite of the high clearing points,they have a remarkably low viscosity and favorable electro-opticalproperties, in particular they permit short switching times, lowthreshold potentials and, depending on the choice of R¹, a modificationof the elastic properties. Further, the optical anisotropy can be variedin a broad range; for example, the compounds of formula I in which ringsA, B and C are trans-1,4-cyclohexylene and/or trans-1,3-dioxane-2,5-diylhave low optical anisotropies and the compounds of formula I in whichrings A, B and C are unsubstituted or fluoro-substituted 1,4-phenylenehave especially high optical anisotropies.

Having regard to the excellent properties, the compounds in accordancewith the invention also offer the possibility of decreasing the numberof components in a mixture and thus of simplifying the mixturesubstantially. In this case it is of advantage that the compounds inaccordance with the invention have a good miscibility with knownmaterials and, having regard to the low melting enthalpies, also have agood solubility in high concentrations.

The above term "fluoro-substituted 1,4-phenylene" embraces in the scopeof the present invention especially 2-fluoro-1,4-phenylene and2,3-difluoro-1,4-phenylene.

The term "1E-alkenyl with 2 to 12 carbon atoms" embraces straight-chainor branched residues, especially the straight-chain residues vinyl,1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl,1E-octenyl, 1E-nonenyl, 1E-decenyl, 1E-undecenyl and 1E-dodecenyl.

The term "3E-alkenyl with 4 to 12 carbon atoms" embraces straight-chainor branched residues, especially the straight-chain residues 3-butenyl,3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 3E-octenyl, 3E-nonenyl,3E-decenyl, 3E-undecenyl and 3E-dodecenyl.

The term "4-alkenyl with 5 to 12 carbon atoms" embraces straight-chainor branched residues, especially the straight-chain residues 4-pentenyl,4-hexenyl, 4-heptenyl, 4-octenyl, 4-nonenyl, 4-decenyl, 4-undecenyl and4-dodecenyl. 4-pentenyl and the Z-isomers of the other named residuesare preferred.

The term "C₁ -C₁₀ -alkyl" embraces straight-chain and branched residues,especially the straight-chain residues methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl and decyl.

The term "saturated ring" denotes in the scope of the present inventiontrans-1,4-cyclohexylene and trans-1,3-dioxane-2,5-diyl. The term"aromatic ring" denotes unsubstituted or fluoro-substituted1,4-phenylene, especially 1,4-phenylene, 2-fluoro-1,4-phenylene and2,3-difluoro-1,4-phenylene.

Compounds of formula I in which R¹ is a straight-chain residue and R² ishydrogen or a straight-chain residue are preferred However, if desired,R¹ and/or R² can have a chain branching. For example, compounds offormula I having a chiral residue R¹ and/or R² are suitable as opticallyactive dopants for the production of cholesteric phases.

In formula I preferably a maximum of one of rings A, B and C (preferablyring A or B) stands for trans-1,3-dioxane-2,5-diyl.

Preferably, the compounds of formula I have a maximum of 1 or 2 lateralfluorine substituents. Any fluorine substituents which may be presentare preferably on ring B or especially on ring C.

A preferred aspect is concerned with those compounds of formula I inwhich ring A is a saturated ring and ring C is an aromatic ring. Wheren=1, ring B can be saturated or aromatic.

A further preferred aspect is concerned with those compounds of formulaI in which rings A and C represent saturated rings. Where n=1, ring B ispreferably also a saturated ring. Especially preferred are thosecompounds in which one of the rings (especially ring A or B) stands fortrans-1,4-cyclohexylene or trans-1,3-dioxane-2,5-diyl and the otherrings stand for trans-1,4-cyclohexylene. These compounds have very lowoptical anisotropies.

Furthermore, those compounds of formula I in which rings A and Crepresent aromatic rings are preferred. Where n=1, ring B is preferablyalso an aromatic ring. These compounds have especially high opticalanisotropies.

Examples of especially preferred sub-groups of compounds of formula Iare the compounds of formulas ##STR4## wherein X¹ and X² eachindependently represent hydrogen or fluorine; R² is hydrogen or C₁ -C₁₀-alkyl; and R¹ denotes 3E-alkenyl with 4 to 12 carbon atoms, 4-alkenylwith 5 to 12 carbon atoms and in formulas I-1, I-2, I-4, I-5, I-6, I-7,I-8, I-9, I-10, I-11, I-14 and I-15 R¹ also is 1E-alkenyl with 2 to 12carbon atoms.

Preferably, R¹ in the above formulas has a maximum of 7 carbon atoms.Residues R¹ with up to 5 carbon atoms are especially preferred.

R² in the above formulas preferably is hydrogen or C₁ -C₅ -alkyl,especially hydrogen or C₁ -C₃ -alkyl.

The compounds of formula I can be manufactured in accordance with theinvention by

a) for the manufacture of the compounds of formula I in which R² ishydrogen, reacting a compound of formula ##STR5## wherein n, R¹ andrings A, B and C have the significances given in formula I, with analkyllithium, or

b) for the manufacture of the compounds of formula I in which R² is C₁-C₁₂ -alkyl, alkylating a compound of formula I in which R² is hydrogen.

The reaction of a compound of formula II with an alkyllithium can beeffected in a manner known per se. Preferred lithium compounds are C₁-C₄ -alkyllithiums such as methyllithium, butyllithium and the like. Thereaction is preferably effected in an inert organic solvent such ashexane, tetrahydrofuran and the like at maximum temperatures of about-70° C.

The alkylation of the compounds of formula I in which R² is hydrogen canbe effected according to usual alkylation methods. According to apreferred method the acetylene compound is deprotonized with a base andthen alkylated with a C₁ -C₁₀ -alkyl halide. The deprotonization can beeffected, for example, with butyllithium, methyllithium, sodium hydrideand the like in an inert organic solvent (e.g. hexane, tetrahydrofuranand the like) at temperatures below about -30° C. The subsequentalkylation step can be carried out, for example, with an alkyl chloride,bromide or iodide in the presence of hexamethylphosphoric acid triamide.

The compounds of formula II are novel. They can be prepared in a mannerknown per se from the cyano compounds of formula ##STR6## wherein n, R¹and rings A, B and C have the significances given in formula I.

For example, a compound of formula III can be reduced withdiisobutylaluminium hydride and the aldehyde obtained can be reactedwith tetrabromomethane and triphenylposphine to give a compound offormula II.

The compounds of formula III are known or are analogues of knowncompounds and can be prepared according to the methods described inEP-A-0122389, EP-A-0167912 and EP-A-0315050.

The compounds of formula I can be used in the form of mixtures with oneanother and/or with other liquid crystal components such as e.g. withsubstances from the classes of Schiff's bases, azobenzenes,azoxybenzenes, phenylbenzoates, cyclohexanecarboxylic acid phenylesters, cyclohexanecarboxylic acid cyclohexyl esters, biphenyls,henylcyclohexanes, cyclohexylcyclohexanes, phenylpyrimidines,cyclohexylpyrimidines, phenyldioxanes, 2-cyclohexyl-1-phenylethanes,terphenyls, cyclohexylbiphenyls, cyclohexylphenylpyrimidines and thelike. Such substances are known to the person skilled in the art andmany of them are, moreover, commercially available.

The liquid crystalline mixtures in accordance with the invention containat least two components, of which at least one component is a compoundof formula I. A second component and optionally further components canbe further compounds of formula I and/or other liquid crystalcomponents.

The compounds of formula I are especially suitable for nematic mixturesor, insofar as at least one component of the mixture is opticallyactive, also for cholesteric mixtures. A preferred field of applicationis their use as dielectrics in liquid crystal indicating devices havinga twisted nematic liquid crystal structure such as TN cells, STN cells,SBE cells and OMI cells. Preferred mixtures are therefore those whichcontain one or more compounds of formula I and one or more compoundshaving positive dielectric anisotropy.

Having regard to the good solubility of the compounds of formula I inother liquid crystal materials and having regard to their goodmiscibility with one another, the amount of the compounds of formula Iin the mixtures in accordance with the invention can be relatively highand can amount to, for example, about 1-70 wt. % or above. In general,an amount of about 3-50 wt. %, especially about 5-30 wt. %, of compoundsof formula I is preferred.

Preferably, the mixtures in accordance with the invention contain, inaddition to one or more compounds of formula I, one or more compoundsfrom the group of compounds of formulas ##STR7## wherein R³ is alkyl,3E-alkenyl or 4-alkenyl; R⁴ represents alkyl, cyano or fluorine; R⁵ andR⁶ denote alkyl or alkoxy; R⁷ and R¹⁰ each independently are alkyl,1E-alkenyl, 3E-alkenyl or 4-alkenyl; R⁸ denotes cyano, alkyl,3E-alkenyl, 4-alkenyl, alkoxy, 2E-alkenyloxy or 3-alkenyloxy; R⁹ isalkoxy, 2E-alkenyloxy or 3-alkenyloxy; n stands for the number 0 or 1; Zrepresents a single covalent bond or --CH₂ CH₂ --; X³ denotes fluorineor chlorine and X⁴ denotes hydrogen, fluorine or chlorine; R¹¹ is alkyl,3E-alkenyl, 4-alkenyl, alkoxy, 2E-alkenyloxy or 3-alkenyloxy; one of thegroups Y¹ and Y² is a single covalent bond, --COO--, --OOC--, --CH₂ CH₂--, --CH₂ O-- or --OCH₂ -- and the other of the groups Y¹ and Y² is asingle covalent bond; rings A¹ and A² each independently representsubstituted or unsubstituted trans-1,4-cyclohexylene in which optionally2 non-adjacent CH₂ groups are replaced by oxygen or substituted orunsubstituted 1,4-phenylene in which optionally 1 CH group or 2 CHgroups is/are replaced by nitrogen; R¹² denotes alkyl or 2-alkenyl; R¹³is 1E-alkenyl, 3E-alkenyl, 4-alkenyl, (2-alkenyl)oxymethyl, alkyl orcyano; and R¹⁴ denotes cyano, alkyl, 1E-alkenyl, 3E-alkenyl, 4-alkenyl,alkoxy, 2E-alkenyloxy or 3-alkenyloxy.

The term "substituted or unsubstituted trans-1,4-cyclohexylene in whichoptionally 2 non-adjacent CH₂ groups are replaced by oxygen" embracesespecially trans-1,4-cyclohexylene and trans-1,3-dioxane-2,5-diyl aswell as rings which are substituted with substituents which are usual inliquid crystals such as cyano, methyl, fluorine or chlorine, for example1-cyano-trans-1,4-cyclohexylene or 2-methyl-trans-1,4-cyclohexylene.

The term "substituted or unsubstituted 1,4-phenylene in which optionally1 CH group or 2 CH groups is/are replaced by nitrogen" embracesespecially 1,4-phenylene, pyridine-2,5-diyl, pyrazine-2,5-diyl andpyrimidine-2,5-diyl as well as rings which are substituted withsubstituents which are usual in liquid crystals such as cyano, methyl,fluorine or chlorine, for example 2-cyano-1,4-phenylene,2-fluoro-1,4-phenylene, 2-chloro-1,4-phenylene or2-methyl-1,4-phenylene.

Preferred mixture components having positive dielectric anisotropy arethe cyano- and halo-compounds of formulas V, VI, VIII, IX, X, XII, XIV,XV, XVI, XIX, XXI and XXIII as well as the isothiocyanates of formulaXXII. Preferably, the final mixture contains about 20-70 wt. %,especially about 25-50 wt. %, of one or more of these compounds.

The mixtures in accordance with the invention can also contain opticallyactive compounds (e.g. optically active 4'-alkyl- or4'-alkoxy-4-biphenylcarbonitriles) and/or dichroic coloring substances(e.g. azo, azoxy or anthraquinone coloring substances). The amount ofsuch compounds is determined by the solubility, the desired pitch,colour, extinction and the like. In general, the amount of opticallyactive compounds and dichroic coloring substances amounts to a maximumof in each case about 10 wt. % in the final mixture.

The manufacture of the mixtures in accordance with the invention and themanufacture of the electro-optical devices can be effected in a mannerknown per se.

The manufacture of the compounds of formula I and of liquid crystallinemixtures containing these compounds are illustrated in more detail bythe following Examples. C is a crystalline phase, S is a smectic phase,S_(A) is a smectic A phase, N is a nematic phase and I is the isotropicphase. V₁₀ denotes the voltage for 10% transmission (viewing directionperpendicular to the surface of the plates). t_(on) and t_(off) denoterespectively the switching-on time and the switching-off time, Δndenotes the optical anisotropy and ΔH denotes the melting enthalpy.

EXAMPLE 1

a) A solution of 9.036 g oftrans-4-[trans-4-(1E-propenyl)cyclohexyl]cyclohexanecarbonitrile in 45ml of toluene was treated dropwise while gassing with nitrogen at 0°-4°C. within 55 minutes with 39 ml of a 20 percent (v/v) solution ofdiisobutylaluminium hydride in toluene. After completion of the additionthe reaction mixture was stirred at 0° C. for a further 15 minutes andthen at room temperature for a further 3.5 hours. Subsequently, thecolourless reaction solution was pipetted into 200 ml of 1N sulphuricacid while cooling with an ice bath and the mixture obtained wasextracted once with 400 ml of methylene chloride and twice with 150 mlof methylene chloride each time. The combined methylene chloride phaseswere washed twice with 150 ml of water each time, dried over sodiumsulphate, filtered and evaporated. There were thus obtained 10.2 g ofcrude trans-4-[trans-4-(1E-propenyl)cyclohexyl]cyclohexanecarboxaldehydeas a colourless oil.

b) A solution of 28.5 g of tetrabromomethane in 519 ml of methylenechloride was treated dropwise while gassing with nitrogen at -15° C.within 13 minutes with a solution of 45.7 g of triphenylphosphine in 97ml of methylene chloride. The orange solution was stirred at about -10°C. for a further 10 minutes and then treated dropwise within 25 minuteswith a solution of 10.2 g oftrans-4-[trans-4-(1E-propenyl)cyclohexyl]cyclohexanecarboxaldehyde in112 ml of methylene chloride and rinsed with 25 ml of methylenechloride. The reaction mixture was stirred at about 0° C. for a further50 minutes and then poured into 3.9 1 of hexane. The mixture was stirredat room temperature for 2.5 hours. Thereafter, the precipitate wasfiltered off under suction and washed with hexane. The filtrate wasconcentrated in a vacuum and the yellowish solid residue obtained (33.4g) was suspended in 2 l of hexane. The suspension was stirred at roomtemperature for 15 minutes and then cooled in an ice bath for 1 hour.Subsequently, the precipitate was filtered off under suction and washedwith about 0.5 1 of cold hexane. The filtrate was concentrated in avacuum. The colourless solid residue (19.2 g, was purified bychromatography on silica gel with hexane at 0.4 bar. There were thusobtained 12.7 g oftrans-4-(2,2-dibromovinyl)-1-[trans-4-(1E-propenyl)cyclohexyl]cyclohexaneas a colourless solid substance.

c) A solution of 12.7 g oftrans-4-(2,2-dibromovinyl)-1-[trans-4-(1E-propenyl)cyclohexyl]cyclohexanein 500 ml of tetrahydrofuran was treated dropwise while gassing withnitrogen at -74° C. within 30 minutes with 49 ml of a 1.6M solution ofbutyllithium in hexane. The yellowish solution was stirred at -74° C.for a further 1 hour, then poured into 500 ml of water and extractedonce with 400 ml of hexane and twice with 200 ml of hexane each time.The combined hexane phases were washed twice with 200 ml of water eachtime, dried over sodium sulphate, filtered and evaporated. There werethus obtained 7.9 g oftrans-4-ethynyl-1-[trans-4-(1E-propenyl)cyclohexyl]cyclohexane ascolourless crystals. Recrystallization from methylene chloride/methanolgave pure product with m.p. (C-N) 45.1° C., cl.p. (N-I) 88.9° C. andΔH=2.323 kcal/mol.

The following compounds can be manufactured in an analogous manner:

trans-4-Ethynyl-1-[trans-4-(3-butenyl)cyclohexyl]cyclohexane, m.p. (C-N)9.0° C. (supercoolable to about -40° C.), cl.p. (N-I) 64.8° C., ΔH=2.280kcal/mol;

trans-4-ethynyl-1-[trans-4-(3E-pentenyl)cyclohexyl]cyclohexane, m.p(C-N) 27.6° C., cl.p. (N-I) 87.7° C., ΔH=3.207 kcal/mol;

trans-4-ethynyl-1-[trans-4-(4-pentenyl)cyclohexyl]cyclohexane, m.p (C-N)12.7° C., cl.p. (N-I) 41.5° C., ΔH=4.526 kcal/mol;

4-ethynyl-1-[trans-4-(1E-propenyl)cyclohexyl]benzene;

4-ethynyl-1-[trans-4-(3E-pentenyl)cyclohexyl]benzene;

4-ethynyl-1-[trans-4-(4-pentenyl)cyclohexyl]benzene;

4'-ethynyl-4-[trans-4-(1E-propenyl)cyclohexyl]biphenyl;

4'-ethynyl-4-[trans-4-(3E-pentenyl)cyclohexyl]biphenyl;

4'-ethynyl-4-[trans-4-(4-pentenyl)cyclohexyl]biphenyl;

4-ethynyl-1-[trans-4-[trans-4-(1E-propenyl)cyclohexyl]cyclohexyl]benzene;

4-ethynyl-4'-(3-butenyl)biphenyl;

4-ethynyl-4'-(4-pentenyl)biphenyl;

4-ethynyl-2,3-difluoro-4'-(3-butenyl)biphenyl;

4-ethynyl-2,3-difluoro-4'-(4-pentenyl)biphenyl;

4-ethynyl-1-[trans-5-(3-butenyl)-1,3-dioxan-2-yl]benzene;

4-ethynyl-1-[trans-5-(4-pentenyl)-1,3-dioxan-2-yl]benzene;

4-ethynyl-4'-[trans-5-(3-butenyl)-1,3-dioxan-2-yl]biphenyl;

4-ethynyl-1-[trans-4-[trans-5-(3-butenyl)-1,3-dioxan-2-yl]cyclohexyl]benzene;

4-ethynyl-1-[trans-5-[trans-4-(1E-propenyl)cyclohexyl]-1,3-dioxan-2-yl]benzene;

4-(trans-4-ethynylcyclohexyl)-1-[trans-5-(1E-propenyl)-1,3-dioxan-2-yl]benzene.

EXAMPLE 2

A solution of 1.0 g oftrans-4-ethynyl-1-[trans-4-(1E-propenyl)cyclohexyl]cyclohexane in 39 mlof tetrahydrofuran was treated dropwise while gassing with nitrogen at-26° C. within 3 minutes with 3.1 ml of a 1.6M solution of butyllithiumin hexane. The yellowish solution was stirred at -20° C. for a further30 minutes, then treated with 4.3 ml of hexamethylphosphoric acidtriamide and subsequently with 0.696 g of propyl bromide. The reactionmixture was stirred at room temperature for a further 3.5 hours, thenpoured into 65 ml of water and subsequently extracted once with 50 ml ofhexane and twice with 40 ml of hexance each time. The combined hexanephases were washed twice with 30 ml of water each time, dried oversodium sulphate, filtered and evaporated. The yellowish nematic crudeproduct (1.186 g) was purified by chromatography on silica gel withhexane at 0.4 bar. There were thus obtained 1.088 g oftrans-4-(1-pentynyl)-1-[trans-4-(1E-propenyl)cyclohexyl]cyclohexane as acolourless nematic substance. Recrystallization from diethylether/methanol gave 0.805 g of pure product with m.p. (C-N) 28.1° C.,cl.p. (N-I) 68.6° C. and ΔH=5.602 kcal/mol.

The following compounds can be manufactured in an analogous manner:

trans-4-(1-Propynyl)-1-[trans-4-(1E-propenyl cyclohexyl]cyclohexane,m.p. (C-N) 69.2° C., cl.p. (N-I) 117.7° C., ΔH=2.310 kcal/mol;

trans-4-(1-butynyl)-1-[trans-4-(1E-propenyl)cyclohexyl]cyclohexane, m.p.(C-N) 26.8° C., cl.p. (N-I) 82.1° C., ΔH=4.430 kcal/mol;

trans-4-(1-propynyl)-1-[trans-4-(3-butenyl)cyclohexyl]cyclohexane, m.p.(C-N) 9.2° C., cl.p. (N-I) 71.5° C.; ΔH=3.714 kcal/mol;

trans-4-(1-butynyl)-1-[trans-4-(3-butenyl)cyclohexyl]cyclohexane, m.p.(C-N) 6.8° C., cl.p. (N-I) 52.5° C., ΔH=4.522 kcal/mol;

trans-4-(1-propynyl)-1-[trans-4-(3E-pentenyl)cyclohexyl]cyclohexane,m.p. (C-N) 47.5° C., cl.p. (N-I) 105.5° C., ΔH=4.594 kcal/mol;

trans-4-(1-butynyl)-1-[trans-4-(3E-pentenyl)cyclchexyl]cyclohexane, m.p.(C-N) 22.8° C., cl.p. (N-I) 86.5° C., ΔH=4.406 kcal/mol;

trans-4-(1-pentynyl)-1-[trans-4-(3E-pentenyl)cyclohexyl]cyclohexane,m.p. (C-N) 35.8° C., cl.p. (N-I) 77.9° C., ΔH=4.160 kcal/mol;

trans-4-(1-hexynyl)-1-[trans-4-(3E-pentenyl)cyclohexyl]cyclohexane, m.p.(C-N) 34.5° C., cl.p. (N-I) 55.5° C., ΔH=5.058 kcal/mol;

trans-4-(1-propynyl)-1-[trans-4-(4-pentenyl)cyclohexyl]cyclohexane, m.p.(C-N) 28.8° C., cl.p. (N-I) 61.3° C., ΔH=5.418 kcal/mol;

trans-4-(1-butynyl)-1-[trans-4-(4-pentenyl)cyclohexyl]cyclohexane, m p.(C-N) 6.6° C., cl.p. (N-I) 44.5° C., ΔH=4.168 kcal/mol;

trans-4-(1-pentynyl)-1-[trans-4-(4-pentenyl)cyclohexyl]cyclohexane, m.p.(C-N) -11.0° C., cl.p. (N-I) 58.9° , ΔH=3.366 kcal/mol;

4-(1-propynyl)-1-[trans-4-(1E-propenyl)cyclohexyl]benzene, m.p. (C-N)69.4° C., cl.p (N-I) 90.7° C., ΔH=4.509 kcal/mol;

4-(1-propynyl)-1-[trans-4-(3E-pentenyl)cyclohexyl]benzene, m.p. (C-N)48.6° C., cl.p. (N-I) 82.5° C., ΔH=3.127 kcal/mol;

4-(1-propynyl)-1-[trans-4-(4-pentenyl)cyclohexyl]benzene, m.p. (C-N)13.9° C., cl.p. (N-I) 31.2° C., ΔH=4.127 kcal/mol;

4'-(1-propynyl)-4-[trans-4-(1E-propenyl)cyclohexyl]biphenyl, m.p. (C-N)189° C., cl.p. (N-I) >300° C. (decomposition), ΔH=5.443 kcal/mol;

4'-(1-propynyl)-4-[trans-4-(3E-pentenyl)cyclohexyl]biphenyl, m.p.(C-S_(A)) 144.8° C., transition S_(A) -N 181.5° C., cl.p. (N-I) >266° C.(decomposition), ΔH=4.490 kcal/mol;

4-(1propynyl)-1-[trans-4-[trans-4-(1E-propenyl)cyclohexyl]cyclohexyl]benzene;

4-(1-propynyl)-4'-(3-butenyl)biphenyl;

4-(1-propynyl)-4'-(4-pentenyl)biphenyl;

4-(1 propynyl)-2,3-difluoro-4'-(3-butenyl)biphenyl;

4-(1-propynyl)-2,3-difluoro-4'-(4-pentenyl)biphenyl;

4-(1-propynyl)-1-[trans-5-(3-butenyl)-1,3-dioxan-2-yl]benzene;

4-(1-propynyl)-1-[trans-5-(4-pentenyl)-1,3-dioxan-2-yl]benzene, m.p.(C-I) 68° C.;

4-(1-propynyl)-4'-[trans-5-(3-butenyl)-1,3-dioxan-2-yl]biphenyl, m.p.(C-N) 116.1° C., S-N 91° C., cl.p. (N-I) 235.7° C., ΔH=4.971 kcal/mol;

4-(1-propynyl)-1-[trans-4-[trans-5-(3-butenyl)-1,3-dioxan-2-yl]-cyclohexyl]benzene,m.p. (C-N) 131.5° C., cl.p. (N-I) 212.3° C., ΔH=7.235 kcal/mol;

4-(1-propynyl)-1-[trans-5-[trans-4-(1E-propenyl)cyclohexyl]-1,3-dioxan-2-yl]benzene;

4-[trans-4-(1-propynyl)cyclohexyl]-1-[trans-5-(1E-propenyl)-1,3-dioxan-2-yl]benzene.

EXAMPLE 3

Several binary mixtures were manufactured from4-(trans-4-pentylcyclohexyl)benzonitrile and in each case one compoundof formula I and the influence on clearing point, V₁₀, t_(on), t_(off)and Δn is investigated. V₁₀, t _(on) and t _(off) were measured at 22°C. in a TN cell having a plate separation of 8 μm, with the 2.5-foldvalue of V₁₀ being chosen as the operating potential. Δn was measured at22° C. The components of formula I used, their concentration in thebinary mixture and the measured data are set forth in Table 1. Thecorresponding values for pure 4-(trans-4-pentylcyclohexyl)benzonitrileare given for comparison.

                                      TABLE 1                                     __________________________________________________________________________    Binary mixture with 4-(trans-4-pentylcyclohexyl)benzonitrile                  Component of formula I,  cl.p. (N-I)                                                                         v.sub.10                                                                          t.sub.on                                                                         t.sub.off                               concentration in wt. %   [°C.]                                                                        [volt]                                                                            [ms]                                                                             [ms]                                                                             Δn                             __________________________________________________________________________    [100% 4-(trans-4-Pentylcyclohexyl)benzonitrile]                                                        54.6  1.62                                                                              30 42 0.120                                10%                                                                              trans-4-Ethynyl-1-[trans-4-(1E-propenyl)-                                                           60.3  1.69                                                                              22 37 0.121                                   cyclohexyl]cyclohexane                                                     20%                                                                              trans-4-Ethynyl-1-[trans-4-(1E-propenyl)-                                                           66.0  1.89                                                                              20 35 0.122                                   cyclohexyl]cyclohexane                                                     10%                                                                              trans-4-(1-Propynyl)-1-[trans-4-(1E-propenyl)-                                                      56.2  1.70                                                                              20 36 0.122                                   cyclohexyl]cyclohexane                                                     20%                                                                              trans-4-(1-Propynyl)-1-[trans-4-(1E-propenyl)-                                                      58.9  1.79                                                                              21 35 0.119                                   cyclohexyl]cyclohexane                                                     10%                                                                              trans-4-(1-Propynyl)-1-[trans-4-(3E-pentenyl)-                                                      57.9  1.62                                                                              22 37 0.122                                   cyclohexyl]cyclohexane                                                     50%                                                                              trans-4-(1-Propynyl)-1-[trans-4-(3E-pentenyl)-                                                      73.1  2.53                                                                              20 34 0.114                                   cyclohexyl]cyclohexane                                                     10%                                                                              trans-4-(1-Butynyl)-1-[trans-4-(1E-propenyl)-                                                       53.9  1.62                                                                              20 36 0.118                                   cyclohexyl]cyclohexane                                                     20%                                                                              trans-4-(1-Butynyl)-1-[trans-4-(1E-propenyl)-                                                       54.2  1.69                                                                              20 36 0.115                                   cyclohexyl]cyclohexane                                                     10%                                                                              4-(1-Propynyl)-1-[trans-4-(1E-propenyl)cyclo-                                                       57.0  1.60                                                                              21 36 0.128                                   hexyl]benzene                                                              50%                                                                              4-(1-Propynyl)-1-[trans-4-(1E-propenyl)cyclo-                                                       69.1  2.29                                                                              16 27 >0.140                                  hexyl]benzene                                                              10%                                                                              4-(1-Propynyl)-1-[trans-4-(3E-pentenyl)cyclo-                                                       61.7  1.73                                                                              21 36 0.336                                   hexyl]benzene                                                              10%                                                                              4-(1-Propynyl)-1-[trans-4-(4-pentenyl)cyclo-                                                        52.7  1.47                                                                              22 39 0.122                                   hexyl]benzene                                                              10%                                                                              4'-(1-Propynyl)-4-[trans-4-(3E-pentenyl)cyclo-                                                      71.3  1.73                                                                              25 40 0.141                                   hexyl]benzene                                                              __________________________________________________________________________

We claim:
 1. A compound of formula ##STR8## wherein n is the number 0 or1; ring A is trans-1,4-cyclohexylene or trans-1,3-dioxane-2,5-diyl;rings B and C each independently are trans-1,4-cyclohexylene,trans-1,3-dioxane-2,5-diyl or unsubstituted or fluoro-substituted1,4-phenylene; R¹ is 1E-alkenyl with 2 to 12 carbon atoms; and R² ishydrogen or C₁ -C₁₀ -alkyl, with the proviso that no more than onetrans-1,3-dioxane-2,5-diyl ring is present.
 2. The compound of claim 1,having the formula ##STR9## wherein X¹ and X² each independently arehydrogen or fluorine; R² is hydrogen or C₁ -C₁₀ -alkyl; and R¹ is1E-alkenyl with 2 to 12 carbon atoms.
 3. The compound of claim 1, havingthe formula ##STR10## wherein X¹ and X² each independently are hydrogenor fluorine; R² is hydrogen or C₁ -C₁₀ -alkyl; and R¹ is 1E-alkenyl with2 to 12 carbon atoms.
 4. The compound of claim 1, having the formula##STR11## wherein X¹ and X² each independently are hydrogen or fluorine;R² is hydrogen or C₁ -C₁₀ -alkyl; and R¹ is 1E-alkenyl with 2 to 12carbon atoms.
 5. The compound of claim 1, having the formula ##STR12##wherein X¹ and X² each independently are hydrogen or fluorine; R² ishydrogen or C₁ -C₁₀ -alkyl; and R¹ is 1E-alkenyl with 2 to 12 carbonatoms.
 6. The compound of claim 1, having the formula ##STR13## whereinX¹ and X² each independently are hydrogen or fluorine; R² is hydrogen orC₁ -C₁₀ -alkyl; and R¹ is 1E-alkenyl with 2 to 12 carbon atoms.
 7. Thecompound of claim 1, having the formula ##STR14## wherein X¹ and X² eachindependently are hydrogen or fluorine; R² is hydrogen or C₁ -C₁₀-alkyl; and R¹ is 1E-alkenyl with 2 to 12 carbon atoms.
 8. The compoundof claim 1, having the formula ##STR15## wherein X¹ and X² eachindependently are hydrogen or fluorine; R² is hydrogen or C₁ -C₁₀-alkyl; and R¹ is 1E-alkenyl with 2 to 12 carbon atoms.
 9. The compoundof claim 1, having the formula ##STR16## wherein X¹ and X² eachindependently are hydrogen or fluorine; R² is hydrogen of C₁ -C₁₀-alkyl; and R¹ is 1E-alkenyl with 2 to 12 carbon atoms.
 10. The compoundof claim 1, having the formula ##STR17## wherein X¹ and X² eachindependently are hydrogen or fluorine; R² is hydrogen or C₁ -C₁₀-alkyl; and R¹ is 1E-alkenyl with 2 to 12 carbon atoms.
 11. The compoundof claim 1, having the formula ##STR18## wherein X¹ and X² eachindependently are hydrogen or fluorine; R² is hydrogen or C₁ -C₁₀-alkyl; and R¹ is 1E-alkenyl with 2 to 12 carbon atoms.
 12. The compoundof claim 1, having the formula ##STR19## wherein X¹ and X² eachindependently are hydrogen or fluorine; R² is hydrogen or C₁ -C₁₀-alkyl; and R¹ is 1E-alkenyl with 2 to 12 carbon atoms.
 13. The compoundof claim 1, having the formula ##STR20## wherein X¹ and X² eachindependently are hydrogen or fluorine; R² is hydrogen or C₁ -C₁₀-alkyl; and R¹ is 1E-alkenyl with 2 to 12 carbon atoms.
 14. The compoundof claim 1, wherein R¹ is 1E-propenyl.
 15. A liquid crystalline mixturehaving at least two components, wherein at least one of such componentsis a compound of the formula ##STR21## wherein n is the number 0 or 1;ring A is trans-1,4-cyclohexylene or trans-1,3-dioxane-2,5-diyl; rings Band C each independently are trans-1,4-cyclohexylene,trans-1,3-dioxane-2,5-diyl or unsubstituted or fluoro-substituted1,4-phenylene; R¹ is 1E-alkenyl with 2 to 12 carbon atoms; and R² ishydrogen or C₁ -C₁₀ -alkyl, with the proviso that no more than onetrans-1,3-dioxane-2,5-diyl ring is present.